2-part reactive urethane resin composition and method for producing thereof

ABSTRACT

Provided is a material having an excellent sound-absorbing performance which can be easily applied to the desired area at the operation site and which can effectively prevent sound leakage 
     The material includes a 2-part reactive urethane resin composition prepared from a polyisocyanate component and a polyol-containing component, wherein the polyol-containing component comprises a polyol component (a), catalysts (b), a foam stabilizer (c), an amine compound having primary or secondary amino groups (d), and carbon dioxide (e). 
     The 2-part reactive urethane resin composition, when cured, is an open-cell soft polyurethane foam, wherein the average sound absorption coefficient of said polyurethane foam is 30% or more, measured in accordance with JIS A 1405-2:2007 for 63 hertz to 5000 hertz.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority under 35 U.S.C. 119 of JapanesePatent Application No. 2018-067401 filed on Mar. 30, 2018 the entirecontent of which is hereby incorporated by reference herein.

TECHNICAL FIELD

The present disclosure relates to a 2-part reactive urethane resincomposition. More specifically, the present disclosure is related to a2-part reactive urethane resin composition characterized in that a mixedreaction solution of polyurethane materials proceeds foaming andreaction of urethane formation and urea formation immediately at thelocation where it is discharged to form a soft polyurethane foam withalmost no flowing, and that the formed foam has excellentsound-absorbing property.

BACKGROUND

Nowadays, there is an increasing demand for a comfortable acousticenvironment in every place of living spaces. For example, there is aneed in general use for reducing intrusion of external sounds,preventing sounds passing between rooms, reducing reverberating soundsby buildings or the like, and taking measures for the sound of rain andthere is a growing demand for sound-absorbing materials for suchpurposes, let alone special quiescent or anechoic rooms in buildings.Additionally, there is a progress for adapting to a comfortable acousticenvironment in other purposes such as vehicle bodies, heavy machineries,electrical generators, office automation equipment, or home electronics.Particular examples of vehicle spaces are represented by automobilecabins or railway vehicle cabins and a wide variety of sound-absorbingmaterials are reported for creating a comfortable acoustic environment.

Most sound-absorbing materials that are currently used are a sheet-formor a fibrous-form product or a panelized material produced in factoriesor the like and they are often cut out into appropriate shapes andamounts and attached or filled into a space where sound absorbency isintended to be applied. However, there is a trouble of cutting out andattaching and there are cases where sound-absorbing performance cannotbe fully demonstrated when filling into spaces since gaps are formedinevitably between the sound-absorbing materials and the peripheralcontacting materials. What is capable of solving such problems is anon-site foaming type sound-absorbing material, the type which thematerial is injected on-site where sound-absorbing performance isintended to be applied and foaming reaction proceeds on the spot (startof reaction, foaming, and completion of reaction). In this case, aseamless construction without gaps is attained by attaching firmly theperipheral materials and the sound-absorbing materials, whereby a moreeffective sound-absorbing performance can be expected. Particularly,conventionally in automobile industry, there has been a need forimproving stiffness of the entire vehicle body and ensuring acomfortable acoustic environment in the living space. In thisconnection, efforts have been made for embedding injection type resinfoaming materials or sound-insulating materials in center pillars havinga closed cross section structure or closed cross section parts withinthe vehicle body framework.

For example, a technique is attempted wherein a thermoset typefoam-forming material (such as an epoxy or a rubber) is attached to aclosed cross section part and then foamed and cured in a coatedincinerator to improve stiffness and sound insulation. However, sincesuch thermoset type foam-forming material is subject to foaming andcuring by using the coated incinerator of the automobile, there is aneed for suppressing the fluctuation in foaming magnification ratio(unfilled spaces can be created or, excessively foamed parts can becreated on the contrary) which is associated with the change ofincinerating temperature, depending on the part to be used, and there isalso a need to fit the shape of the foam-forming material to the shapeof the closed cross section.

In this regard, as a method for foaming and curing under normaltemperature mixing, a technique is attempted by using a 2-part reactiveurethane resin composition consisted of a main polyol agent and apolyisocyanate curing agent, which is capable of foaming a urethane foamby reaction under a blowing agent (conventionally, exclusively water, orhydrogen atom containing halogenated hydrocarbon systems or low boilingpoint hydrocarbons used alternatively or in combination) and subjectsaid composition to injection, foaming and curing to providereinforcement and sound-insulating effect. This injection technique maysolve the problem of the above-stated fluctuation in foaming or thelike, however, since the injection is performed in a fluidized state,the resin reactant often leaks from the small gaps (or the pore parts)present in the closed cross section. Therefore, there is a need forcreating some kind of a seal or a measure by, for example, adjusting thepolyurethane composition.

Patent Literature 1 reports a technique wherein a urethane materialmixed solution is discharged in froth state to a gap of a body of anautomobile to reduce leakage from opening parts and a polyurethane foamis filled in to specific parts only. However, no specific Examples areshown therein and leakage from the opening parts cannot be sufficientlyhandled just with the technique relying on the froth method and whichdoes not involve reactive adjustment for urethanization. Further, nocharacteristic value of the polyurethane foam is shown which makes itunclear what kind of sound-absorbing property can be expected.

Patent Literatures 2 and 3 report a technique wherein a polyurethanefoam is formed by using a specific amount of specific amines andpromoting reactivity of 2-part reactive urethanization to suppressleakage from gaps or pore parts. However, this technique is solelyrelated to a rigid polyurethane foam having a hydroxyl number from 150to 800 mg KOH/g of the base polyol which is insufficient forsound-absorbing performance. Further, the density of the product(specific gravity of 0.4 in the Example) is not as low as the levelobtainable from the current market.

Patent Literature 4 describes a method for forming a rigid polyurethanefoam wherein a carbamate of alkanolamine (an adduct of alkanolamine andcarbon dioxide) or a mixture of a carbamate of alkanolamine and water asa blowing agent is used, the rigid polyurethane foam having opencavities and connected to automobile parts which are built up on a carbody or a car frame. However, since this method is again related to arigid polyurethane foam, sound-absorbing performance is not enough.Further, the density of the product (from 192 to 384 kg/m3 in theExample) is not as low as the level obtainable from the current market.Generally, it is said that when acoustic waves enter into porousmaterials such as the urethane foam, the aerial vibration thereof willdirectly propagate through the air in gaps and bubbled parts inside thematerial and when they hit against a cell film, the film surfacevibrates to convert a part of sound energy into thermal energy therebygenerating sound-absorbing action. Accordingly, in order to provideexcellent sound-absorbing property, there is a need for softness so thatthe cell film will vibrate and since the conversion level from airvibration into thermal energy is low in the rigid foams, it is notpossible to attain sufficient sound-absorbance.

Under these technical conditions, there is still a need for creating amaterial having excellent sound-absorbing performance which can beeasily injected into a desired area at the operation site and which iscapable of preventing sound leakage.

RELATED ART DOCUMENTS Patent Documents

Patent Document 1 Japanese Unexamined Patent Application Publication No.S61-116509

Patent Document 2 Japanese Unexamined Patent Application Publication No.H10-212332

Patent Document 3 Japanese Unexamined Patent Application Publication No.H11-105057

Patent Document 4 Japanese Unexamined Patent Application Publication No.2007-528434

SUMMARY

The present disclosure is intended to provide a material havingexcellent sound-absorbing performance which can be easily applied to adesired area at the operating site and which is capable of effectivelypreventing sound leakage. The present disclosure is also intended toprovide a material which satisfies both excellent sound absorbency andlow density and which is highly suitable in operations.

The inventors have found that when a 2-part reactive urethane resincomposition prepared from a combination of specific material componentswas applied at the operation site, a foam can be easily formed at thedesired area and sound leakage can be notably prevented. Further, theinventors found that the above-described foam is not only excellent insound-absorbency but is also low in density, highly suitable inoperations and producible efficiently and easily on site. The presentdisclosure is based upon such findings.

Means for Solving the Problems

According to the present disclosure, the following are provided. (1) A2-part reactive urethane resin composition prepared from apolyisocyanate component (X) and a polyol-containing component (Y),

wherein the polyol-containing component (Y) comprises a polyol component(a), catalysts (b), a foam stabilizer (c), an amine compound havingprimary or secondary amino groups (d), and carbon dioxide (e);

said 2-part reactive urethane resin composition when cured being anopen-cell soft polyurethane foam, wherein the average sound absorptioncoefficient of said polyurethane foam is 30% or more, measured inaccordance with JIS A 1405-2:2007 for 63 hertz to 5000 hertz; and

the length of liquid-dripping is within 300 mm measured in accordancewith the following method:

measuring method: an acrylic plate is placed vertically at the position10 cm away from the discharge position of an injection molding machine,and said a mixture of the polyisocyanate component (X) and thepolyol-containing component (Y) is discharged from the injection moldingmachine to the acrylic plate for 0.2 seconds at a rate of 120 g/sec toform an injected product on the acrylic plate; then, 5 minutes afterdischarge, the length from the highest point to the lowest point in thevertical direction of the injected product on the acrylic board ismeasured as the liquid-dripping length.

(2) The 2-part reactive urethane resin composition according to (1),wherein the amine compound comprises aliphatic amines, aromatic amines,or alicyclic amines.(3) The 2-part reactive resin composition according to (1) or (2),wherein the molecular weight of the amine compound is from 33 to 220.(4) The 2-part reactive resin composition according to any of (1) to(3), wherein the amine compound has primary or secondary amino groups.(5) The 2-part reactive urethane resin composition according to any of(1) to (4), wherein the content of the amine compound is from 1 to 15parts by mass based on 100 parts by mass of the polyol component (a).(6) The 2-part reactive urethane resin composition according to any of(1) to (5), wherein the content of said carbon dioxide is from 0.5 to 5parts by mass based on 100 parts by mass of the polyol component (a).(7) The 2-part reactive urethane resin composition according to any of(1) to (6), wherein the content of amine carbonate formed of the aminecompound and carbon dioxide is from 1.5 to 20 parts by mass based on 100parts by mass of the polyol component (a).(8) The 2-part reactive urethane resin composition according to any of(1) to (7), wherein the polyisocyanate component (X) is at least oneselected from the group consisting of diphenylmethane diisocyanate,polymethylene polyphenyl polyisocyanate, and modifications thereof.(9) The 2-part reactive urethane resin composition according to any of(1) to (8), wherein cream time of the mixture of the polyisocyanatecomponent (X) and the polyol-containing component (Y) is 1 second orless.(10) The 2-part reactive urethane resin composition according to any of(1) to (9), wherein the core density of the polyurethane foam is from 10to 110 kg/m³.(11) The 2-part reactive urethane resin composition according to any of(1) to (10), wherein the aeration volume of the polyurethane foam isfrom 3 to 60 L/min, measured in accordance with JIS K 6400-7:2012.(12) The 2-part reactive urethane resin composition according to any of(1) to (11), wherein the average diameter of the cell size of thepolyurethane foam is 400 nm or less.(13) The 2-part reactive urethane resin composition according to any of(1) to (12), wherein the average diameter of the cell size of thepolyurethane foam is 350 nm or less.(14) The urethane resin composition according to any of (1) to (13),wherein the average sound absorption coefficient of the polyurethanefoam is 40% or more, measured in accordance with JIS A 1405-2:2007 for500 hertz to 2500 hertz.(15) The 2-part reactive urethane resin composition according to any oneof (1) to (14), which is prepared by injecting the mixture of thepolyisocyanate component (X) and the polyol-containing component (Y)from the injection molding machine.

According to the present disclosure, a soft polyurethane foam havingexcellent sound absorbency can be easily formed at the desired area atthe operation site by using a 2-part reactive urethane resin compositionwhich has excellent sound absorbency and which the liquid does not dripexcessively upon injection. According to the present disclosure, since asoft polyurethane foam having a sound-absorbing property from 500 to2500 Hz especially required for an acoustic environment for vehiclecabins, can be injected into the desired area by injection molding, itcan be utilized advantageously for creating an excellent acousticenvironment for vehicle cabins.

According to the present disclosure, a soft polyurethane foam ofexcellent sound absorbency and low density can be produced effectivelyand easily at the desired area. Therefore, it can be utilizedadvantageously for satisfying both the improvement of sound-insulationand weight saving for applicable base substrates, represented by vehiclebodies.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic figure illustrating the method for measuring theliquid-dripping of the 2-part reactive urethane resin composition,according to the present disclosure.

FIG. 2 is a graph showing the results by measuring the sound absorptioncoefficient in the Examples, according to the present disclosure.

DETAILED DESCRIPTION 2-Part Reactive Urethane Resin Composition

The 2-part reactive urethane resin composition according to the presentdisclosure is characterized that it is prepared from a polyisocyanatecomponent (X) and a polyol-containing component (Y), wherein thepolyol-containing component (Y) comprises a polyol component (a),catalysts (b), a foam stabilizer (c), an amine compound having primaryor secondary amino groups (d), and carbon dioxide (e); said 2-partreactive urethane resin composition when cured being an open-cell softpolyurethane foam, wherein the average sound absorption coefficient ofsaid polyurethane foam is 30% or more, measured in accordance with JIS A1405-2:2007 for 63 hertz to 5000 hertz; and the length ofliquid-dripping is within 300 mm measured in accordance with thefollowing method: measuring method: an acrylic plate is placedvertically at the position 10 cm away from the discharge position of aninjection molding machine, and a mixture of the polyisocyanate component(X) and the polyol-containing component (Y) is discharged from theinjection molding machine to the acrylic plate for 0.2 seconds at a rateof 120 g/s to form an injected product on the acrylic plate; then, 5minutes after discharge, the length from the highest point to the lowestpoint in the vertical direction of the injected product on the acrylicboard is measured as the liquid-dripping length.

It was unexpected that the 2-part reactive urethane resin compositioncan be produced which the liquid does not excessively drip uponinjection and which forms a polyurethane foam having excellent soundabsorbency by the use of the polyisocyanate component (X) and thepolyol-containing component (Y) comprising an amine component and carbondioxide as the constructing material, as like the present invention.

DISCLOSURE Polyisocyanate Component (X)

Polyisocyanate component (X) used for the urethane stock according tothe present disclosure is not particularly limited and include, forexample, aromatic, cycloaliphatic, and aliphatic polyisocyanates having2 or more isocyanate groups; a mixture of 2 or more of saidpolyisocyanates; and modified polyisocyanates obtained by modifyingthereof, or the like.

Specific examples of polyisocyanate component (X) includetolylenediisocyanate (TDI), diphenylmethanediisocyanate (MDI),polymethylenepolyphenylpolyisocyanate (so-called: crude MDI),xylenediisocyanate (XDI), isophoronediisocyanate (IPDI),hexamethylenediisocyanate (HMDI), or the like. Specific examples ofmodified polyisocyanates include prepolymer type modifications of theabove-described polyisocyanates, nurate modifications, ureamodifications, and carbodiimide modifications, or the like. Amongstthem, MDI, crude MDI or modifications thereof are preferred. Using themis preferable in view of improving foam stability and durability andcost, or the like.

The viscosity (mPa*s/25° C.) of the polyisocyanate component of thepresent disclosure is not particularly limited and preferably is from 50to 2,000, more preferably from 100 to 1,000, further preferably from 120to 500.

The specific gravity of the polyisocyanate component (X) is notparticularly limited and can be, for example, from 1.1 to 1.25.

Polyol-Containing Component (Y)

Polyol-containing component (Y) according to the present disclosurecomprises a polyol component (a), catalysts (b), a foam stabilizer (c),an amine compound having primary or secondary amino groups (d), andcarbon dioxide (e). Polyol component (a)

Polyol component (a) is preferably a polyether carbonate polyol and morepreferably a polyoxyalkylene polyol. According to a particularlypreferred embodiment of the present disclosure, the polyol has anaverage functionality of 2 to 4 and a hydroxyl number from 20 mg to 100mg KOH/g.

The average functionality of the polyol component (a) is preferably from2 to 4 and more preferably from 2 to 3 as mentioned above. Here, theaverage functionality used in the present disclosure refers to thenumber of functional groups per 1 molecule and means the mean value ofthe number of active hydrogen in the initiator. The averagefunctionality of the polyol component (a) within the above range will beadvantageous for avoiding a defect where the physicality, such aspermanent deformation by dry heat compression of the polyurethane foamsis significantly reduced. The average functionality of the polyolcomponent (a) within the above range is also preferable for avoidingphysicality deterioration of, for example, tensile strength, due to thereduced elongation of the obtained polyurethane foam resulting in higherhardness.

The hydroxyl number of the polyol component (a) is preferably from 20 to100 mg KOH/g, more preferably from 25 to 90 mg KOH/g, further preferablyfrom 25 to 80 mg KOH/g. 20 mg KOH/g or more of the hydroxyl number ofthe polyol component (a) is advantageous for suppressing collapse or thelike and stably producing the polyurethane foam molded article. 100 mgKOH/g or less of the hydroxyl number of the polyol will not compromisethe softness of the polyurethane foam and is preferable for obtainingsound-absorbing performance. In this context, a “hydroxyl number”according to the present disclosure is the number of potassium hydroxidein mg required for acetylating hydroxyl groups contained in 1 g of asample (solid portion). This can be calculated from the followingformula after acetylating the hydroxyl groups in the sample using aceticacid anhydride and titrating the unused acetic acid with a potassiumhydroxide solution:

a hydroxyl number [mg KOH/g]=[((A−B)×f×28.05)/S]+acid value

A: an amount of 0.5 mol/l potassium hydroxide ethanol solution used in ablank test (ml)

B: an amount of 0.5 mol/l potassium hydroxide ethanol solution used fortitration (ml)

f: a factor

S: a collected amount of a sample (g)

The polyol component (a) can be produced by known means in the art usingpolymerization units such as initiators, polymerization catalysts, andalkylene oxides. The polymerization catalysts used in the production ofthe polyols include alkali metal catalysts, cesium catalysts,phosphate-based catalysts, multi metal cyanide complex catalysts (DMCcatalysts), or the like.

As for the initiator used for producing the polyol component (a), acompound having 2 or 3 active hydrogens in a molecule is used alone orpreferably used in a combination. Specific examples of a compound having2 active hydrogens include ethylene glycol, propylene glycol,1,4-butanediol, diethylene glycol, and dipropylene glycol. Specificexamples of a compound having 3 active hydrogens include glycerin andtrimethylol propane.

Preferably, alkylene oxides are used as a ring-opening additionpolymerization unit for polyol component (a), as mentioned above.Alkylene oxides include ethylene oxide, propylene oxide,1,2-epoxybutane, 2,3-epoxybutane, or the like and propylene oxide or acombination of propylene oxide and ethylene oxide is preferred. Whenpropylene oxide and ethylene oxide are used in combination, each may beseparately subjected to ring-opening addition polymerizationsequentially to form a block polymeric chain, or, a mixture of propyleneoxide and ethylene oxide may be subjected to ring-opening additionpolymerization to form a random polymeric chain. Further, formations ofthe random polymeric chain and block polymeric chain may be combined.When a block polymeric chain is formed, the order of ring-openingaddition polymerization is preferably the order from propylene oxide toethylene oxide, or the order by firstly adding ethylene oxide and thenadding in the order propylene oxide and ethylene oxide.

Other types may be a polyester polyol obtainable from reaction ofpolycarboxylic acid and a low-molecular weight compound containinghydroxyl groups, a polycarbonate polyol obtained from ring-openingpolymerization of caprolactone, or a polyether polyamine obtained byaminating hydroxyl groups of a polyether polyol or by hydrolyzingisocyanate prepolymers of a polyether polyol.

One kind of the polyol component (a) may be used or 2 or more kinds maybe combined.

The content of the polyol component (a) in the polyol-containingcomponent (Y) is preferably from 50 to 100% by mass, more preferablyfrom 50 to 90% by mass, further preferably from 70 to 90% by mass, basedon 100% by mass of the polyol-containing component (Y).

Catalysts (b)

A suitable example of catalysts (b) in the polyol-containing componentaccording to the present disclosure includes urethane catalysts.Urethane catalysts are advantageous for reacting polyols withpolyisocyanate components. All kinds of catalysts that promoteurethanization reaction can be used for the urethane catalysts, forexample, tertiary amines such as triethylenediamine,dimethylaminoethanol, bis(2-dimethylaminoethyl)ether, andN,N,N′,N′-tetramethylhexamethylenediamine; carboxylic metal salts suchas potassium acetate and potassium 2-ethylhexanoate; and organicmetallic compounds such as stannous octoate and dibutyl tin dilaurate.The amount of the catalysts may be from 0.1 to 5 parts by mass based on100 parts by mass of the polyol component.

Foam Stabilizer (c)

The polyol containing composition according to the present disclosuresuitably contains a foam stabilizer (c) in view of forming good cells inthe polyurethane foam. The cell geometry of the sound-absorbing softpolyurethane foam suitable for the present disclosure can be adjusted byappropriately determining the type, the combination and the amount to beused of the foam stabilizer. Preferably, the average cell size and theaeration volume are appropriately adjusted by using the foam stabilizerin order to provide excellent sound-absorbing property, let aloneprevent the foams from collapsing or shrinking after foaming.

One kind of the foam stabilizer (c) may be used or may be a compositionby combining 2 or more components. Specific examples of the foamstabilizer (c) include silicone based foam stabilizers orfluorine-containing compound based foam stabilizers and silicone basedfoam stabilizers are preferable. According to a preferred embodiment ofthe present disclosure, the silicone based foam stabilizers are siliconefoam stabilizers having a polyoxyalkylene-dimethylpolysiloxane copolymeras the main component. Such silicone based foam stabilizers may includethe polyoxyalkylene-dimethylpolysiloxane copolymer alone or othercomponents may be combined thereto. Other combined components may beexemplified as a polyoxyalkylmethylsiloxane, glycols or apolyoxyalkylene compound, or the like. According to another preferredembodiment of the present disclosure, the foam stabilizer (c) is also acomposition comprising 2 or more kinds selected from apolyoxyalkylene-dimethylpolysiloxane copolymer, apolyalkylmethylsiloxane, and an alkylene oxide compound. Such compoundsare especially advantageous in view of foam stability. Examples ofcommercially available products of the foam stabilizer (c) include tradenames of the following: L-580, L-590, L-620, L-680, L-682, L-690,SC-154, SC-155, SC-240, L-598, L-2100, L-2171, SH-210, L-2114, SE-232,L-533, L-534, L-539, M-6682B, L-626, L-627, L-3001, L-3111, L-3415,L-3002, L-3010, L-3222, L-3416, L-3003, L-3333, L-3417, L-2171, L-3620,L-3630, L-3640, L-3170, L-3360, L-3350, L-3555, L-3167, L-3150/L-3151,L-5309, SH-209, and L-3184 manufactured by MOMENTIVE. Examples of othercommercially available products include trade names of the following:SF-2964, SF-2962, SF-2969, SF-2971, SF-2902L, SF-2904, SF-2908, SF-2909,SRX-274C, SZ-1328, SZ-1329, SZ-1330, SZ-1336, SZ-1346, SZ-3601,SRX-294A, SRX-280A, SRX-294A, SRX-298, SH-190, SH-192, and SH-194manufactured by Toray Dow Corning. Examples of other commerciallyavailable products include trade names of the following: F-327, F-345,F-305, and F-242T manufactured by Shin-Etsu Chemical Co., Ltd. or tradenames of the following: Silbyk 9700, Silbyk 9705, and Silbyk 9710manufactured by BYK Chemie. Also included are B4113, B4900, B8002,B8110, B8123, B8228, B8232, B8715LF2, B8724LF2, BF2370, and BF2470manufactured by EVONIC.

The content of the foam stabilizer in the polyol containing compositionmay be appropriately selected and preferably is from 0.1 to 10 parts bymass based on 100 parts by mass of the polyol component.

Amine Compound Having Primary or Secondary Amino Groups (d)

Amine compound (d) according to the present disclosure may function as across-linking agent in the 2-part reactive composition. Therefore, theamine compound (d) is preferably an amine cross-linking agent.

The amine compound (d) according to the present disclosure is preferablyaliphatic amines, aromatic amines, or alicyclic amines having primary orsecondary amino groups, or the like.

Suitable examples of the aliphatic amine compounds having primary orsecondary amino groups include alkylamine compounds such asethylenediamine, m-xylene diamine, 1,4-diaminohexane, butylamine,hexamethylene diamine, diethylene triamine, triethylene tetramine, anddimethylamino propylamine; alkanolamine compounds such as ethanol amine,N-methylethanol amine, diethanol amine, isopropanol amine, anddiisopropanol amine; and hydroxyl

Suitable examples of the aromatic amine compounds having primary orsecondary amino groups include 3,5-diethyl-2,4(or 2,6)-diaminotoluene(DETDA), 2-chloro-p-phenylenediamine, 3,5-dimethylthio-2,4 (or2,6)-diaminotoluene, 1-trifluoromethyl-3,5-diaminobenzene,1-trifluoromethyl-4-chloro-3,5-diaminobenzene, 2,4-toluenediamine,2,6-toluenediamine, bis(3,5-dimethyl-4-aminophenyl)methane, and4,4-diaminodiphenylmethane.

Suitable examples of the alicyclic amine compounds having primary orsecondary amino groups include amino groups such as1,3-bis(aminomethyl)cyclohexane and isophorone diamine; and/or cycloalkanes having 2 or more amino alkyl groups.

The content of the amine compound (d) is from 1 to 10 parts by massbased on 100 parts by mass of the polyol component (a). From 2 to 9parts by mass is preferable and from 3 to 8 parts by mass is morepreferable. 1 parts by mass or more of the content is preferable forensuring liquid-dripping of the polyurethane foam. 10 parts by mass orless of the content is preferable in view of considering stabilizationwhen the foam is formed (collapse or shrinkage are generated in the foamwhen it becomes unstable) and also for cost saving for production of thefoams by the use of amine compounds in small amounts.

Carbon Dioxide (e)

Carbon dioxide (e) according to the present disclosure contributes tothe foam formation at the earliest stage, immediately after the 2-partis reacted and injected and it may function as a blowing agent in the2-part reactive composition.

The content of carbon dioxide is from 0.5 to 5 parts by mass based on100 parts by mass of the polyol component (a). From 1 to 5 parts by massis preferable and from 2 to 5 parts by mass is more preferable. 0.5parts by mass or more of the content is preferable in view of ensuringliquid-dripping and low density of the polyurethane foam. 5 parts bymass or less of the content is preferable in view of consideringstabilization when the foam is formed (collapse or shrinkage aregenerated in the foam when it becomes unstable).

Carbon dioxide may be in the form of liquid or gas. When carbon dioxideis in the form of liquid, it can be added to the polyol-containingcomponent (Y) as it is together with other material components such asthe polyol component (a) if desired. When carbon dioxide is in the formof gas, it can be added to the polyol-containing component (Y) byintroducing into a sealed container such as a tank, together with othermaterial components, and applying pressure. When carbon dioxide is addedto the polyol-containing component (Y) within the container such as atank, this is possible by substituting gas inside the tank by carbondioxide, then increasing the tank pressure to about 2-5 kgf/cm² andmoderately stirring the polyol-containing component (Y) in the tank.

The amount of dissolved carbon dioxide can be obtained by measuring thedensity of the polyol-containing component (Y) under atmosphericpressure, in accordance with the following formula.

$\begin{matrix}{{{Dissolved}\mspace{14mu} {carbon}\mspace{14mu} {dioxide}\mspace{14mu} {amount}\mspace{14mu} \left( {{weight}\mspace{14mu} \%} \right)} = {\frac{\left( \begin{matrix}{\left( {{density}\mspace{14mu} {of}\mspace{14mu} {fresh}\mspace{14mu} {polyol}\mspace{14mu} {containging}\mspace{14mu} {component}\mspace{14mu} (Y)} \right) -} \\\left( {{density}\mspace{14mu} {of}\mspace{14mu} {polyol}\mspace{14mu} {containing}\mspace{14mu} {component}\mspace{14mu} (Y)\mspace{14mu} {after}\mspace{14mu} {dissolution}} \right)\end{matrix} \right.}{\begin{pmatrix}{{density}\mspace{14mu} {of}\mspace{14mu} {polyol}\mspace{14mu} {containing}} \\{{component}\mspace{14mu} (Y)\mspace{14mu} {after}\mspace{14mu} {dissolution}}\end{pmatrix}} \times \frac{44 \times 100}{22400}}} & {{Formula}\mspace{14mu} 1}\end{matrix}$

As for other blowing agents of carbon dioxide, water, hydrofluorocarbonHFC or the like which is a Freon based blowing agent, orhydrofluoroolefin HFO (1233zd, 1336mzz) or the like may be used.

Water can contribute to the formation of the polyurethane foams byemitting carbon dioxide after reacting with the polyisocyanate component(X). Using water is especially advantageous for reducing the density ofthe polyurethane foams. Water is used in amounts of preferably from 0 to10 parts by mass, more preferably from 4 to 6 parts by mass, based on100 parts by mass of the polyol component (a). Using water in amounts of0 parts by mass or more is preferable for reducing the density of thepolyurethane foam and using in amounts of 10 parts by mass or less ispreferable for ensuring stability of the polyurethane foam at the timeof molding.

Adduct of Amine Compound Having Primary or Secondary Amino Groups andCarbon Dioxide

An amine compound having primary or secondary amino groups (d) andcarbon dioxide (e) are known to easily initiate an addition reaction toform an adduct of an amine compound having primary or secondary aminogroups and carbon dioxide (also called “amine carbonate salts”)(e.g.Japanese Unexamined Patent Application Publication No. S62-220512). Forthe composition according to the present disclosure, amine carbonatesalts can be used as a material in which an amine compound and carbondioxide are incorporated. The reaction of amine carbonate salts with thepolyisocyanate is extremely quick, thus the urea formation reaction canbe initiated immediately along with emission of carbon dioxide.Therefore, amine carbonate salts can contribute to the foaming formation(the so-called “froth formation”) at the earliest stage immediatelyafter the reaction and discharge of the mixture of the polyisocyanatecomponent (X) and the polyol-containing component (Y).

The synthesis of amine carbonate salts can be prepared by referring tothe method described in Japanese. For example, they can be easilysynthesized in a relatively short period by heating the amine compoundto 30-110° C., preferably 50-80° C., and blowing in carbon dioxide undera condition of 1-5 bar with slow stirring. Normally, at the stage where1 mol of carbon dioxide is absorbed into 2 amine equivalent of the aminecompound, the reaction terminates and heat generation stops. Since thisreaction solution sometimes solidifies at normal temperature, in orderto avoid this, liquid-form polyols, ethylene glycol or the like may beadded to the amine compound in advance.

In the present disclosure, amine carbonate salts may be formed duringthe production step of the polyol-containing component (Y). According toone embodiment, the polyol-containing component (Y) is obtainable frommixing amine carbonate salts formed of the amine compound and carbondioxide, and raw components of the polyol-containing component (Y) otherthan the amine compound and carbon dioxide. Further, according toanother embodiment, carbon dioxide and raw components of thepolyol-containing component (Y) containing the amine compound are mixedto obtain the polyol-containing component (Y) and amine carbonate saltscan be generated in the polyol-containing component (Y).

With respect to the molar ratios of the amine compound and carbondioxide, in order to obtain function as a sufficient blowing agent, themolar ratio of carbon dioxide is preferably from 0.3 to 0.5 mol, morepreferably from 0.4 to 0.5 mol, to 1 mol of the amino groups. Also forthe primary or secondary amine compounds having 2 or more amino groups,the molar ratio of carbon dioxide is preferably from 0.3 to 0.5 mol to 1mol of the amino groups.

In the polyol-containing component (Y) according to the presentdisclosure, the content of the adduct of the amine compound havingprimary or secondary amino groups and carbon dioxide is from 3 to 20parts by mass, preferably from 4 to 18 parts by mass, more preferablyfrom 5 to 15 parts by mass, based on 100 parts by mass of the polyolcomponent (a). 3 parts by mass or more of the content of theabove-described adduct is preferable for preventing foamability of theinitial polyurethane foam from decreasing and preventing liquid leakageat the time of filling the vehicle body framework. Further, 20 parts bymass or less of the content of the above-described adduct is preferablein view of considering stabilization when the foam is formed (collapseor shrinkage are generated in the foam when it becomes unstable) andalso for cost saving for production of the foams by the use of aminecompounds in small amounts.

When in the case where amine carbonate salts are used, water or carbondioxide may be used in combination as a further blowing agent. However,in view of density control, it is preferable to use water and aminecarbonate salts only. The use of only water and amine carbonate salts isadvantageous for accurately predicting the foaming amount and obtainingfoams having stable density and quality.

Other Components

A desired component other than the components mention above may befurther blended into the urethane stock when producing the polyurethanefoams according to the present disclosure. Additives include fillerssuch as potassium carbonate or barium sulfate; surfactants such asemulsifiers; antiaging agents such as antioxidants or ultravioletabsorbing agents; flame retardants; plasticizers; colorants; antifungusagents; foam breakers; dispersing agents; discoloration inhibitors orthe like.

In view of ensuring safety, a flame retardant may be contained in thepolyol-containing component (Y) according to the present disclosure, ifdesired. The flame retardane is preferably a phorphorous flame retardantand suitable examples are tricresyl phosphate (TCP), triethyl phosphate(TEP), tris(β-chloroethyl)phosphate (TCEP),tris(β-chloropropyl)phosphate (TCPP), or the like. One kind of the flameretardant may be used or multiples thereof may be used in combination.Examples of other flame retardants are metal oxides (for example, ironoxides, titanium oxides, and cerium oxides), metal hydroxides (forexample, aluminum hydroxides), bromine-based compounds (for example,brominated diphenyl ether, brominated diphenyl alkane, and brominatedphthalimide), phosphorous compounds (for example, red phosphorus,phosphoric ester, phosphoric ester salts, amide phosphate, and organicphosphine oxides), and nitric compounds (for example, ammoniumpolyphosphate, phosphagene, triazine, and melamine cyanurate). Theseflame retardants may be used alone or multiples thereof may be used incombination.

If necessary, a so called cross-linking agent of relatively lowmolecular weight, having polyisocyante reactive active hydrogens can beblended in.

The cross-linking agent includes a compound having 2 or more hydroxylgroups. Suitable cross-linking agent is a compound having an averagefunctionality from 2.0 to 8.0 and a hydroxyl number from 200 to 2,000 mgKOH/g. One kind of the cross-linking agent may be used or 2 or morekinds may be used in combination. More particular examples of thecross-linking agent will be described below.

The cross-linking agent having hydroxyl groups is a preferably acompound having from 2 to 8 hydroxyl groups and include polyvalentalcohols, low-molecular weight polyoxyalkylene polyols obtainable byadding alkylene oxides to polyvalent alcohols, and polyols havingtertiary amino groups (amine compounds having primary or secondary aminogroups are excluded).

Particular examples of the cross-linking agent having hydroxyl groupsinclude ethylene glycol, 1,4-butanediol, neopentyl glycol,1,6-hexanediol, diethylene glycol, triethylene glycol, dipropyleneglycol, triethanol amine, glycerin, sorbitol, sucrose, pentaerythritol,N-alkyldiethanol, a bisphenol A-alkylene oxide adduct, aglycerine-alkylene oxide adduct, a trimethylolpropane-alkylene oxideadduct, a pentaerythritol-alkylene oxide adduct, a sorbitol-alkyleneoxide adduct, a sucrose-alkylene oxide adduct, an aliphaticamine-alkylene oxide adduct, an alicyclic amine-alkylene oxide adduct, aheterocyclic polyamine-alkylene oxide adduct, an aromatic amine-alkyleneoxide adduct, polyols of natural origin, or the like.

Isocyanate Index

The 2-part reactive urethane resin composition according to the presentdisclosure can be prepared from the polyisocyanate component (X) and thepolyol-containing component (Y) as mentioned above. Preferably, the usedamount of the polyisocyanate component (X) and the polyol-containingcomponent (Y) is an amount in which the proportion of thepolyol-containing component (Y) and the polyisocyanate component (X) inthe raw materials is from 80 to 120 in isocyanate index. Isocyanateindex can be expressed by [(the ratio of the equivalent amount of theisocyanate groups in the polyisocyanate component to the equivalentamount of active hydrogens in the polyol-containing component)×100].

Method for Production/Polyurethane Foam Molding Machine

The 2-part reactive urethane resin composition according to the presentdisclosure can be injected with an injection molding machine and curedto form a soft polyurethane foam. Therefore, the method for producingthe urethane resin composition according to the present disclosurecomprises a step of injecting a mixture of the polyisocyanate component(X) and the polyol-containing component (Y) from an injection moldingmachine. The injection molded machine used for producing thepolyurethane foam molded article is not particularly limited and amolded machine of a 2-part mixing type (and a mixing type of 3 or moreparts) which is known in the art can be used. Such molding machineincludes for example, high-pressure polyurethane molding machines orlow-pressure polyurethane molding machines, represented by reactiveinjection molding machines manufactured by Canon, Hennecke, orPolyurethane Engineering. Mixing method of the 2 parts in such moldingmachines are not particularly limited and various methods can be used.Exemplified is a method for mechanical stirring by use of stirringblades or the like, a method by static mixers, a method in which 2-partcomponents are opposed and collided under high pressure and theturbulent flow of the liquid in a cavity causes the mixing, or the like.A spraying machine of a 2-part mixing type can also be used. In thepresent disclosure, the 2-part mixed urethane resin composition isdischarged from a molding machine at the site necessary to form thepolyurethane foam.

In the production method according to the present disclosure, thetemperature of the raw materials of the polyisocyanate component (X) andthe polyol-containing component (Y) at the time of injection is notparticularly limited, as long as the formation of the polyurethane foamsis not interfered, and for example, is from 20 to 60° C., preferablyfrom 30 to 50TC.

The discharged amount of the polyisocyanate component (X) and thepolyol-containing component (Y) may be appropriately set respectively,depending on the size of the applicable substrate and reactivity of theraw materials, and for example, is from 1 to 2000 g/sec, preferably from10 to 1000 g/sec.

According to the production method of the present disclosure, the 2-partreactive urethane resin composition which is obtainable from thepolyisocyanate component (X) and the polyol-containing component (Y) inthe injection step is cured to form an open-cell soft polyurethane foam.Therefore, according to one embodiment, there is provided a compositionfor producing the 2-part reactive urethane resin composition togetherwith the polyisocyanate component (X) comprising the polyol-containingcomponent (Y), According to another embodiment, there is also provided acomposition for producing the 2-part reactive urethane resin compositiontogether with the polyol-containing component (Y) comprising thepolyisocyanate component (X). According to the present disclosure, asound-absorbing polyurethane foam can be formed rapidly at the operationsite through the reaction of urethane formation and the urea formationof the 2-part reactive urethane resin composition, along withsuppression of liquid-dripping. Thus, there is an advantage thatexcellent sound absorbency is easily provided at the desired region.

Function/Application Liquid-Dripping

Method to measure liquid-dripping of the 2-part reactive urethane resincomposition according to the present disclosure is as follows.

Measuring method: an acrylic plate is placed vertically at the position10 cm away from the discharge position of an injection molding machine,and the mixture the polyisocyanate component (X) and thepolyol-containing component (Y) is discharged from the injection moldingmachine to the acrylic plate for 0.2 seconds at a rate of 120 g/sec toform an injected product on the acrylic plate; then, 5 minutes afterdischarge, the length from the highest point to the lowest point in thevertical direction of the injected product on the acrylic board ismeasured as the liquid-dripping length. Further details of the measuringmethod can be performed in accordance with the Examples described below.

The length of liquid-dripping of the 2-part reactive urethane resincomposition according to the present disclosure is preferably within 300mm, more preferably from 50 to 300 mm, further preferably from 70 to 280mm. Setting such range for the length of liquid-dripping is advantageousfor adding the composition at the operation site at a desired positionand arranging the polyurethane foams.

Reactivity

Cream time, gel time, and rise time of the 2-part reactive urethaneresin composition according to the present disclosure are preferably inshort time, in view of suppressing liquid-dripping and forming thepolyurethane foam rapidly. In this context, cream time refers to thetime period from the time in which mixing of the polyol-containingcomponent and the polyisocyanate component has started, calling thistime 0 second, to the time in which change of the color phase starts tohappen in said mixed solution and foaming is initiated. Gell time (inseconds) refers to the period in which the mixed solution of thepolyol-containing component and the polyisocyanate component is cured(the time until the solution starts to get stringy when touched with astick-like solid). Rise time (in seconds) refers the time until foamingterminates in the above-stated mixed solution (the time until the riseby foaming of the foam surface stops). In the present disclosure, creamtime, gel time, and rise time are according to the mean value of timemeasurement by visual judgment with stirring by trained, specializedpanelists (n=10).

More particularly, cream time of the 2-part reactive urethane resincomposition according to the present disclosure is preferably 2 secondsor less, further preferably 1 second or less. Gel time of theabove-stated composition is preferably 25 seconds or less, morepreferably from 5 to 21 seconds, further preferably from 7 to 10seconds. Rise time of the above-stated composition is preferably 50seconds or less, further preferably 40 seconds or less.

Continuous Foaming Soft Polyurethane Foam

The polyurethane foam formed by curing of the 2-part reactive urethaneresin composition according to the present disclosure is an open-cellfoaming soft polyurethane foam, as mentioned above. In this context, a“continuous foaming soft polyurethane foam” according to the presentdisclosure means that at least one part of the cells (foams) in thepolyurethane foam is continuous, instead of all the cells, andindependent air bubbles may be present in the polyurethane foam. In thepresent disclosure, it is possible to set the aeration volume, softness,and restoration of the polyurethane foams obtainable in the presentdisclosure in a wide range by controlling the proportion of thecontinuous foams and the independent foams in the polyurethane foam inan appropriate manner. Therefore, according to the preferred embodimentof the present disclosure, continuous air bubbles and individual airbubbles are coexisting in view of ensuring air permeability, softness,and restoration.

Sound-Absorbing Property

When the 2-part reactive urethane resin composition according to thepresent disclosure cures to form the soft polyurethane foam, the averagesound absorption coefficient of such soft polyurethane foam ispreferably 40% or more, more preferably from 45 to 99%, measured inaccordance with JIS A 1405-2:2007 for 500 hertz (Hz) to 2500 hertz (Hz).Using a polyurethane foam having such average sound absorptioncoefficient is especially advantageous for selectively absorbingundesired sound and noise entering from outside without interruptingconversations in a vehicle cabin environment.

The peak top in sound absorption coefficient of the above-described softpolyurethane foam measured in accordance with JIS A 1405-2:2007 ispreferably in the range between 500 hertz and 2500 hertz, morepreferably in between 500 hertz and 2000 hertz. Although in typical softpolyurethane foams, absorption peaks or the main absorption range aremostly found in the area above 2500 Hz, according to the presentdisclosure, the peak top in sound absorption coefficient of thepolyurethane foam set in the above-stated range will allow realizing agood acoustic environment in vehicles or rooms.

Average Cell Size and Aeration Volume

When the 2-part reactive urethane resin composition according to thepresent disclosure cures to form the soft polyurethane foam, the softpolyurethane foam can be provided with a cell geometry of an open-cell.

In order to obtain sufficient sound-absorbing performance, a cellgeometry is preferred in which sound goes through between the cells forthe longest distance possible when passing through the polyurethane foamand during such period, sound is reflected diffusely, then distributedand absorbed. The 2-part reactive urethane resin composition accordingto the present disclosure is especially advantageous for attaining thecell size and the aeration volume suitable for sound absorption asmentioned above in the polyurethane foam. The cell size and the aerationvolume can be adjusted by adjusting the respective raw materialcomponents such as the foam stabilizer, the polyisocyanate component,the polyol component, amines, catalysts as mentioned above and thecondition thereof, or the like, in an appropriate manner.

The average cell size (diameter) in the polyurethane foam according tothe present disclosure is preferably from 100 to 400 m, more preferablyfrom 100 to 350 m. The average cell size of 100 μm or more isadvantageous in preventing the foams to be molded from shrinking. Theaverage cell size of 400 μm or less is advantageous for the sound topass through the foams in an appropriate distance and exhibitingexcellent sound-absorbing property.

The aeration volume in the polyurethane foam according to the presentdisclosure is preferably from 3 to 60 L/min, more preferably from 4 to50 L/min. 3 L/min or more of the aeration volume is advantageous inpreventing the foams to be molded from shrinking. 60 L/min or less ofthe aeration volume is advantageous in exhibiting excellentsound-absorbing property.

Applicable Substrate

In the present disclosure, the above-stated 2-part reactive urethaneresin composition is discharged on to a desired substrate having “opencavities” and by undergoing the reaction comprising foaming and curing,the polyurethane foam can be molded in the substrate. In this context,“an open cavity” means the opened-part to the air which can be used as afilling opening when filling the urethane resin composition into thesubstrate. The shapes and the arrangement of the substrate are notparticularly limited, as long as it has the open cavities (openedparts). In particular, shapes may be of a substantially plain area, acurved area, a hollow space in the part, or other appropriate shapes.Since the urethane resin composition according to the present disclosurehas small liquid-dripping, substrates can be used which are evenincapable of holding fluid due to those shapes or arrangements.

Sound-Absorbing Material Purposes

The 2-part reactive urethane resin composition according to the presentdisclosure can be suitably used as a sound-absorbing material in theabove-described applicable substrate. Suitable applicable substratesinclude vehicle bodies and parts thereof, heavy machineries, electricalgenerators, office automation equipment, home electronics, constructionmembers, or the like, and vehicle bodies (especially of automobiles) orconstruction members are especially preferred. Vehicle body frameworkmembers are preferred as the vehicle body part and include pillars,sills (locking panels), and chassis rails. The urethane resincomposition according to the present disclosure can be suitably appliedto the vehicle body parts in assembly lines of the vehicle bodies asvehicle body framework filling materials, especially in the productionof the vehicle bodies.

EXAMPLES

The disclosure will be explained in detail by the aid of the Examplesbelow without being limited by these Examples. Numerical values to beused will represent parts by mass, unless otherwise specified. Units andmeasuring methods are in accordance with JIS (Japanese IndustrialStandards) unless otherwise specified.

Comparative Example 1

A rigid urethane polyurethane foam was produced similar to thosedescribed in Example 1 of Japanese Patent Laid-Open Publication No.2015-4011. The raw materials used are compounds as follows.

Raw Materials of Polyol-Containing Component

Polyol A1: 1.6 mol of formaldehyde and 2.4 mol of diethanol amine, basedon 1 mol of nonylphenol, were reacted to obtain a Mannich compound 1. Tothis Mannich compound 1, propylene oxide (PO) and ethylene oxide (EO)were subjected to ring-opening addition polymerization in this order toobtain a Mannich polyol having a viscosity of 800 mPa·s at 25° C. and ahydroxyl number of 300 mg KOH/g. The ratio of EO to the total amount ofPO and EO was 70% by weight at this time.

Polyol B1: Glycerine was used as an initiator and propylene oxide (PO)and ethylene oxide (EO) were subjected to ring-opening additionpolymerization in this order to obtain a polyetherpolyol having aviscosity of 800 mPa·s at 25° C. and a hydroxyl number of 35 mg KOH/g.The ratio of EO to the total amount of PO and EO was 15% by weight atthis time.

Polyol C1: Pentaerythritol was used as an initiator and only propyleneoxide was subjected to ring-opening addition polymerization to obtain apolyetherpolyol having a viscosity of 1800 mPa·s at 25° C. and ahydroxyl number of 370 mg KOH/g.

Catalyst 1: trade name TOYOCAT-RX3, manufactured by TOSOH Corporation (afoaming, reactive catalyst)

Catalyst 2: trade name TOYOCAT-RX7, manufactured by TOSOH Corporation (afoaming, reactive catalyst)

Foam Stabilizer 1: trade name SF-2937, manufactured by Toray Dow Corning

Foam Stabilizer 2: trade name SH-194, manufactured by Toray Dow Corning

Flame Retardant: tris(2-chloropropyl)phosphate (trade name: TMCPP,manufactured by DAIHATI CHEMICAL INDUSTRY CO., Ltd.)

Polyisocyanate: polymeric MDI trade name: Sumidule 44V20L (manufacturedby Sumika Bayer Urethane Co., Ltd.) viscosity (25° C.) 180 mPa·s, NCOcontent: 31.5%

Polyisocyanate

polymethylene polyphenyl polyisocyanate manufactured by Sumika CovestroUrethane Co., Ltd.

Using the above described raw materials, a polyol-containing componentwas prepared with the formula as shown below, and the polyol-containingcomponent and polyisocyanate were mixed for reaction at liquidtemperature of 40° C., room temperature of 20° C., and a volume ratio of1:1 using a spray foaming machine to produce a rigid foam in accordancewith JIS-A-9526.

Polyol A1: 70 parts by mass

Polyol B1: 20 parts by mass

Polyol C1: 10 parts by mass

Water: 17 parts by mass

Catalyst 1: 7 parts by mass

Catalyst 2: 3 parts by mass

Foam Stabilizer 1: 2 parts by mass

Foam Stabilizer 2: 2 parts by mass

Flame Retardant: 40 parts by mass

Examples 1 to 11 and Comparative Examples 2 and 3

The polyol mixtures comprising the polyol compounds, catalysts, the foamstabilizers, amine carbonate salts and water as the blowing agents andthe polyisocyanate compounds were mixed and reacted with a high-pressurefoaming machine to form polyurethane foams. Soft polyurethane foams wereproduced with the formulae as shown in Table 1.

The raw materials used in the Examples and the Comparative Example 2 and3 are as follows.

Polyisocyanate

x1: polymethylene polyphenyl polyisocyanate manufactured by SumikaCovestro Urethane Co., Ltd.viscosity (25° C.) 180 mPa·s, NCO content: 31.5%

Polyol

a1: Polyetherpolyol having an average functionality of 3 and a viscosityof 1600 mPa·s at 25° C. and a hydroxyl number of 28 mg KOH/g, obtainedby ring-opening addition polymerization of alkyleneoxide.

Catalysts

b1: Dabco33LV (manufactured by EVONIK)b2: dimethylaminoethanolb3: Toyoat ET (manufactured by TOSOH Corporation)b4: dibutyl tin dilaurate

Foam Stabilizer

c1: Tegostab B8724LF2 (manufactured by EVONIK)

Amine Cross-Linking Agent

d1: monoethanolamined2: diethanolamined3: diethyltoluenediamined4: Ethacure 300 (manufactured by Albemarle)

Blowing Agent

e1: watere2: carbon dioxidee3: amine carbonate salts consisted of monoethanolamine and carbondioxide (molar ratio of the amine compound and carbon dioxide is 1:0.5)

Molding Conditions

Foaming machine: A-system 40Std (manufactured by Cannon)Temperature of raw materials: polyol-containing component/polyisocyanatecomponent=30-50° C./30-50° C.Discharged amount per second: 120 g/secDischarge pressure: polyol-containing component/polyisocyanatecomponent=13 MPa/13 MPaMixing ratio: polyol-containing component/polyisocyanatecomponent=100/42.4-115 (mass ratio)(isocyanate index as 100)Discharge outlet diameter: 1 cm in diameter (0.785 cm²)

Each evaluation was performed under the following methods. The resultsare shown in Table 1.

<Reactivity>

The filling time was set to 0.6 seconds under the molding conditions asdescribed in Table 1, 72 g of urethane mixed solution was introduced into a 1 L cup, and cream time, gel time, rise time were measured. Thetime when the mixing of the polyol system liquid and the polyisocyanatewas commenced was called zero second, and the time until foaming startswas called cream time, the time until the foaming body starts to getstringy when lightly poking the foaming body with a chopstick andpulling out the chopstick from the foaming body was called gel time, thetime until the rise of the foam due to foaming stops was called risetime, and each were measured visually (unit: second(s)).

<Shrinkage and Corruption>

In the above-stated reactivity measurement, those which maintained thefoam shape after rise time was expressed as “None” and those whichshrunk was “Yes”. When they collapsed, they were expressed as“Collapsed”.

<Core Density>

The filling time was set to 1.2 seconds under the molding conditions asdescribed in Table 1, 144 g of urethane mixed solution was introduced into an upper face-opened type mold of 200×200×50 mm, and 50 mm×50 mm×30mm was cut out from the center of the free foamed foam, and density wascalculated from the weight.

<Aeration Volume>

The filling time was set to 1.2 seconds under the molding conditions asdescribed in Table 1, 144 g of urethane mixed solution was introduced into an upper face-opened type mold of 200×200×50 mm, 51 mm×51 mm×25 mmwas cut out from the center of the free foamed foam, and the aerationvolume was calculated by using a device in accordance with JIS K6400-7:2012.

<Sound Absorbency>

The filling time was set to 1.2 seconds under the molding conditions asdescribed in Table 1, 144 g of urethane mixed solution was introduced into an upper face-opened type mold of 200×200×50 mm, Φ40 mm×30 mm was cutout from the center of the free foamed foam, and sound absorbency wasmeasured by using a vertically-directed sound absorption coefficientmeasuring system WinZacMTX manufactured by NihonOnkyo Engineering Co.,Ltd. in accordance with JIS A 1405-2:2007. The value obtained bydividing the sum of sound absorption coefficient in the prescribedfrequency range (63-5000 Hz) by the number of measurement was namedaverage sound absorption coefficient 1. The value obtained by dividingthe sum of sound absorption coefficient in the prescribed frequencyrange (500-2500 Hz) by the number of measurement was named average soundabsorption coefficient 2.

<Liquid-Dripping>

Liquid-dripping was measured in accordance with the method as shown inthe schematic figure in FIG. 1. In particular, an acrylic plate wasplaced vertically at the position 10 cm away from the discharge positionof an injection molding machine, and the 24 g of the above-described2-part mixture was discharged from the injection molding machine to theacrylic plate for 0.2 seconds at a rate of 120 g/sec to form an injectedproduct on the acrylic plate. 5 minutes after discharge, the length fromthe highest point to the lowest point in the vertical direction of theinjected product on the acrylic board was measured as theliquid-dripping length. Together, the width and the height of theinjected product (the foam) were also measured. Those which dribbleddown from the acrylic plate were determined as fallen off. The detailsof the molding conditions were in accordance with Tables 1 and 2.

<Average Cell Size>

Rectangular solids in 100×50×30 (t) mm were cut out from the centerparts of the foams obtained from the Examples or the ComparativeExamples. Then, SEM pictures (magnification ratio of 40, name ofphotographic device:desktop electron scanning microscope NeoScope™JCM-6000, company name JEOL Ltd.) were taken for the cross-sectionalsurfaces of the rectangular solids and cell conditions were observed.The cell conditions were evaluated by specialized panelists (10 people).With respect to distribution, 50 cells were selected evenly from thewhole area of the observed area and each cell diameter was measured. Asfor the average diameter, the average value of the cell diameters wasshown.

TABLE 1 Comparative Comparative Example 1 Example 2 Example 1 Example 2Example 3

 Component*2 x1 pbw Described Above 88  98  106  106  Polyol- Polyol a1pbw 100  100  100  100  containing Catalysts b1 pbw   0.4   0.4   0.4  0.4 Component Y b2 pbw   0.5   0.5   0.5   0.5 b3 pbw 1   0.2 1   0.5b4 pbw   0.05 —   0.05    0.05 Foam Stabilizer c1 pbw 1 1 1  1 BlowingAgents e1 pbw 6 6 6  6 e2 pbw 2 1 2  2 Amine d1 pbw 6 3 6  6 Compoundsd2 pbw — — — — d3 pbw — — — — d4 pbw — — — — Notes *2  *2  *2  *2Molding Raw Material Polyisocyanate ° C. 30 30  30  30  50 ConditionsComponent X Temperature Polyol-containing ° C. 30 30  30  30  50Component Y Reactivity Cream Time sec —  1>  1>  1>  1> Gel Time sec — 721  5   2.5 Rise Time sec — 14  31  12  12 Foam PropertyShrinkage(Yes/None)or None None None None None None CollapseLiquid-dripping — — Fell off ◯ ◯ ◯ Liquid-dripping mm — — 337  150  149 (Length) Core Density

20 26  37  25  25 Aeration Volume

10 — 4 20  24 Average Cell Size nm 250  — 350  230  270  Average sound %15 — 44  40  31 absorption coefficient 1 (63-5000 Hz) Average sound % 10— 65  42  41 absorption coefficient 2 (500-2500 Hz) Peak Top Position ofHz 3150  — 1000   1250   1250  Sound-absorbance Comparative ComparativeExample 3 Example 4 Example 5 Example 6 Example 4

 Component*2 x1 pbw 106  31  38 38 63   Polyol- Polyol a1 pbw 100  100 100  100  100    containing Catalysts b1 pbw   0.4   0.4   0.4   0.4 0.4Component Y b2 pbw   0.5   0.5   0.5   0.5 0.5 b3 pbw   0.2   0.2   0.2  0.2 0.2 b4 pbw   0.05 — — — — Foam Stabilizer c1 pbw   0.1 1  1  1 1  Blowing Agents e1 pbw 5 6  6  6 6   e2 pbw 2 2  3   4.7 5.1 Amine d1 pbw5 6  6 14 16   Compounds d2 pbw — — — — — d3 pbw — — — — — d4 pbw — — —— — Notes *2  *2  *2 *2 *2   Molding Raw Material Polyisocyanate ° C.30  30  30 30 30   Conditions Component X Temperature Polyol-containing° C. 30  30  30 30 30   Component Y Reactivity Cream Time sec  1>  1> 1>  1> 1>  Gel Time sec 5 9  8  7 6   Rise Time sec 12  14  13 12 10  Foam Property Shrinkage(Yes/None)or None None None None None CollapseCollapse Liquid-dripping — ◯ ◯ ◯ ◯ — Liquid-dripping mm 205  175  150 135  — (Length) Core Density

25  104  89 86 — Aeration Volume

380  18  34 55 — Average Cell Size nm 1220   130  150  150  — Averagesound % 20  35  45 43 — absorption coefficient 1 (63-5000 Hz) Averagesound % 17  50  60 60 — absorption coefficient 2 (500-2500 Hz) Peak TopPosition of Hz 4000   1000   1250  1250  — Sound-absorbance ExampleExample Example 7 Example 8 Example 9 10 11

 Component*2 x1 pbw 82 94 103  91 90 Polyol- Polyol a1 pbw 100  100 100  100  100  containing Catalysts b1 pbw   0.4   0.4   0.4   0.4   0.4Component Y b2 pbw   0.5   0.5   0.5   0.5   0.5 b3 pbw   0.2   0.2  1 1  1 b4 pbw — —    0.05    0.05    0.05 Foam Stabilizer c1 pbw  1  1  1 1  1 Blowing Agents e1 pbw  4  5  6  6  6 e2 pbw  2  2  2  2  2 Amined1 pbw  6  6 — — — Compounds d2 pbw — —  6 — — d3 pbw — — —  6 — d4 pbw— — — —  6 Notes *2 *2 *3 *3 *3 Molding Raw Material Polyisocyanate ° C.30 30 30 30 30 Conditions Component X Temperature Polyol-containing ° C.30 30 30 30 30 Component Y Reactivity Cream Time sec  1>  1>  1>  1>  1>Gel Time sec  7  8  5  6  6 Rise Time sec 17 13 12 14 14 Foam PropertyShrinkage(Yes/None)or None None None None None None CollapseLiquid-dripping — ◯ ◯ ◯ ◯ ◯ Liquid-dripping mm 230  225  170  152  185 (Length) Core Density

36 31 25 24 25 Aeration Volume

26 30 22 17 15 Average Cell Size nm 280  310  250  310  290  Averagesound % 38 39 35 45 33 absorption coefficient 1 (63-5000 Hz) Averagesound % 51 52 41 45 40 absorption coefficient 2 (500-2500 Hz) Peak TopPosition of Hz 800  1000  — — — Sound-absorbance *1 Parts by mass ofpolyisocyanate based on 100 parts by mass of polyol-containing component(isocyanate index 100). *2 Amine Carbonate Salts, used as e3 *3 CarbonDioxide dissolved in polyol-containing component

 in tank container.

indicates data missing or illegible when filed

It can be understood from Comparative Example 1 in Table 1 that therigid polyurethane foam of all water blown foam which is a heatinsulating material for houses showed no liquid-dripping or shrinkagedue to its rapid reactivity and continuous foaming, however, due to itsrigidness, it had lower sound-absorbing performance than the softpolyurethane foam (Example 1) in all the frequency areas. This was alsoshown in sound absorption coefficient of FIG. 2. Further, in FIG. 2, thepeak tops (1250 Hz) of Example 1, Example 7 and Example 8 was shifted tothe shorter frequency range compared with that of Comparative Example 1.Though not shown in FIG. 2, the other Examples also showed the sametendency as Example 1 in terms of sound absorption coefficient as wellas peak top.

In Comparative Example 2 shown in Table 2, the amine compound was notused and liquid dripped even by adjusting reactivity to become rapid andrise time to 14 seconds, resulting in falling of the foam. InComparative Example 3, the cells closed in the soft polyurethane foamdue to the addition of the amine compound in large amounts of 16 partsby mass and a problem arose in which the polyurethane foam shrunk.

On the other hand, in Examples 1 and 2, evaluation was performed with 6parts by mass of water as the blowing agent and 3 and 6 parts by mass ofthe amine compound (4 and 8 parts by mass as amine carbonate salts).Both reactivity and foam property were good.

In Example 3, although the formulation was the same as Example 2,molding was performed by increasing the liquid temperature of thepolyol-containing component and the polyisocyanate component to 50° C.However, a foam was able to be formed without being in a shrunk or acollapsed state which allowed to confirm the stable formability of thissystem.

In Comparative Example 3, the larger the aeration volume or the averagecell size became, the more the average sound absorption coefficientdecreased. This demonstrated that it is important to adjust the aerationvolume or the average cell size in order to obtain excellentsound-absorbing property.

In Examples 4, 5, and 6, no water as the blowing agent was used but onlyamine carbonate salts and foaming was performed by changing the amountthereof to 8-18.7 parts by mass. These were good in both reactivity andfoam property. However, when the amount of amine carbonate salts was 21parts by mass, shrinkage occurred in the foam as shown in ComparativeExample 4.

In Examples 7 and 8, water as the blowing agent was used in 4 and 5parts by mass respectively and both reactivity and foam property weregood.

In Examples 9, 10, and 11, it was confirmed that a similar effect wasobtainable as the earlier Examples by compounding the amine compound andcarbon dioxide individually into the polyol-containing component, evenwithout using amine carbonate salts in which the amine compound andcarbon dioxide are integrated.

INDUSTRIAL APPLICABILITY

According to the present disclosure, a soft polyurethane foam havingexcellent sound-absorbing performance can be applied for on-sitefoaming. Additionally, it is suitable for wide applications for on-sitefoaming of constructions, construction materials, vehicle bodies or thelike since the reaction mixture solution completes foaming immediatelyat the place being discharged without flowing and also has low densityand high productivity.

1. A 2-part reactive urethane resin composition prepared from apolyisocyanate component (X) and a polyol-containing component (Y),wherein the polyol-containing component (Y) comprises a polyol component(a), catalysts (b), a foam stabilizer (c), an amine compound havingprimary or secondary amino groups (d), and carbon dioxide (e); said2-part reactive urethane resin composition when cured being an open-cellsoft polyurethane foam, wherein an average sound absorption coefficientof said polyurethane foam is 30% or more, measured in accordance withJIS A 1405-2:2007 for 63 hertz to 5000 hertz; and wherein a length ofliquid-dripping for the 2-part reactive urethane resin composition is300 mm or less measured in accordance with the following measuringmethod: an acrylic plate is placed vertically at a position 10 cm awayfrom the discharge position of an injection molding machine, and amixture of the polyisocyanate component (X) and the polyol-containingcomponent (Y) is discharged from the injection molding machine to theacrylic plate for 0.2 seconds at a rate of 120 g/sec to form an injectedproduct on the acrylic plate; then, 5 minutes after discharge, thelength from the highest point to the lowest point in the verticaldirection of the injected product on the acrylic board is measured asthe liquid-dripping length.
 2. The 2-part reactive urethane resincomposition according to claim 1, wherein the amine compound comprisesaliphatic amines, aromatic amines, or alicyclic amines.
 3. The 2-partreactive resin composition according to claim 1, wherein the molecularweight of the amine compound is from 33 to
 220. 4. The 2-part reactiveresin composition according to claim 1, wherein the amine compound hasprimary or secondary amino groups.
 5. The 2-part reactive urethane resincomposition according to claim 1, wherein the content of the aminecompound is from 1 to 15 parts by mass based on 100 parts by mass of thepolyol component (a).
 6. The 2-part reactive urethane resin compositionaccording to claim 1, wherein the content of said carbon dioxide is from0.5 to 5 parts by mass based on 100 parts by mass of the polyolcomponent (a).
 7. The 2-part reactive urethane resin compositionaccording to claim 1, wherein the content of amine carbonate formed ofthe amine compound and carbon dioxide is from 1.5 to 20 parts by massbased on 100 parts by mass of the polyol component (a).
 8. The 2-partreactive urethane resin composition according to claim 1, wherein thepolyisocyanate component (X) is at least one selected from the groupconsisting of diphenylmethane diisocyanate, polymethylene polyphenylpolyisocyanate, and modifications thereof.
 9. The 2-part reactiveurethane resin composition according to claim 1, wherein cream time ofthe mixture of the polyisocyanate component (X) and thepolyol-containing component (Y) is 1 second or less.
 10. The 2-partreactive urethane resin composition according to claim 1, wherein thecore density of the polyurethane foam is from 10 to 110 kg/m³.
 11. The2-part reactive urethane resin composition according to claim 1, whereinan aeration volume of the polyurethane foam is from 3 to 60 L/min,measured in accordance with JIS K 6400-7:2012.
 12. The 2-part reactiveurethane resin composition according to claim 1, wherein an averagediameter of a cell size of the polyurethane foam is 400 nm or less. 13.The 2-part reactive urethane resin composition according to claim 1,wherein an average diameter of a cell size of the polyurethane foam is350 nm or less.
 14. The 2-part reactive urethane resin compositionaccording to claim 1, wherein an average sound absorption coefficient ofthe polyurethane foam is 40% or more, measured in accordance with JIS A1405-2:2007 for 500 hertz to 2500 hertz.
 15. The 2-part reactiveurethane resin composition according to claim 1, which is prepared byinjecting the mixture of the polyisocyanate component (X) and thepolyol-containing component (Y) from the injection molding machine.